Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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SOLID-STATE ADDITIVE MANUFACTURING METHODS FOR COMPOUNDING
CONDUCTIVE POLYMER COMPOSITIONS,
FABRICATION OF CONDUCTIVE PLASTIC PARTS AND CONDUCTIVE COATINGS.
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The present application relies on the disclosure of and claims
priority to and the benefit
of the filing date of U.S. Provisional Application Nos. 62/729,836, filed
Sept. 11, 2018, and
62/740,758, filed Oct. 3, 2018, each of which is hereby incorporated by
reference in their entireties.
BACKGROUND OF THE INVENTION
Field of the Invention
[0002] The present invention is directed to the field of solid-state
additive manufacturing.
More particularly, embodiments of the invention relate to methods of solid-
state additive
manufacturing of products with one or more conductive polymer. Embodiments
also relate to
methods of solid-state additive manufacturing which incorporate plastic waste
as feed material.
The methods are performed with a solid-state additive manufacturing machine
which includes one
or more of a feeding unit, a spindle, a tool, a motor, a driving unit, a
control unit, a monitoring
unit, a power supply and a process control software; wherein the spindle and
the tool each have an
internal passageway indirectly or directly in operable communication with each
other for a filler
material to pass from the feeding unit through the internal passageways of the
spindle and tool to
a workpiece. The solid-state additive manufacturing machine generates severe
plastic deformation
of the filler material by applying normal, shear and/or frictional forces by
way of a rotating
shoulder of the tool such that the filler material is in a malleable and/or
visco-elastic state in an
interface region, thereby producing a formed conductive polymer or plastic
composition or 3D
printed layer or object with incorporated plastic waste. Embodiments also
relate to products
produced by the disclosed methods.
Description of Related Art
[0003] Conductive Plastics
[0004] Plastics are typically electrically- and thermally- insulating
materials. The interest in
conductive plastics has been prompted by numerous advantages which these
plastics offer in
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comparison to metals, such as tunable conductivity, lighter weight, inherent
corrosion/oxidation
resistance, a wide range of available properties, design flexibility and good
processability
(including printing in desirable 3D-shapes), scalability, economics (lower
cost than metals and
machined parts; lower shipping costs), and recycling opportunity.
[0005] In many applications, the fabrication of conductive plastic parts is
preferred due to their
light weight and affordability which results from the elimination of secondary
processes often
required in metal processing. Also, most plastics are resistant to denting,
chipping, scratching,
corrosion and chemicals.
[0006] Electrically Conductive Plastics
[0007] Plastics charge very easily due to their insulating nature; even
when grounded, the
plastic material stays charged with static electricity. Charged plastic
materials could cause a risk
for uncontrolled electrostatic discharge (ESD). Even grounding would not
remove the electrical
charges from a common (insulating) plastic material. Conductive plastic
compounds, unlike
insulating plastics, have the ability to conduct electricity. When grounded,
conductive plastics
remain in zero potential as they do not accumulate static electricity. Over
the years, electrically
conducting polymers have been developed by adding conductive fillers, such as
carbon black,
graphite, metallic fibers, flakes, carbon fibers and nano-size fillers, such
as carbon nanotubes and
metal nanoparticles.
[0008] The use of plastic materials is restricted in applications in which
uncontrolled
electrostatic discharges must be prevented and eliminated. Non-charging (i.e.
dissipative)
conductive plastic compounds ensure safe dissipation of electrical charges.
One of the largest
application areas for electrically conductive plastic compounds is found in
the electronics industry.
For instance, in electronics production, the most critical production steps
are performed in a special
ESD Protected Area (EPA). Inside the EPA, all the objects as well as workers
must be grounded
to the same potential. All of the plastic parts inside the EPA should be
composed of electrically
conductive plastic compounds. Electrically conductive plastic compounds are
also required for the
packaging of sensitive electronics components, and are also used in aerospace
components,
medical devices, and the automotive, computer and appliance industries;
specific applications
include automotive fuel systems, conductive storage containers for inks and
hazardous liquids, in
medical devices, e.g. aerosol devices, where such plastics ensure that an
aerosol device dispenses
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a full dose of a powder or a liquid without the substances adhering to the
device itself. A defined
range of plastics conductivity is required for control units, sensors and
enclosures.
[0009] Other uses of electrically conductive plastics include electrostatic
discharge (ESD)
control and electromagnetic interference (EMI) shielding applications.
Electromagnetic (EM)
shielding is the practice of surrounding electronics and cables with
conductive or magnetic
materials to guard against incoming or outgoing emissions of electromagnetic
frequencies (EMF).
EM shielding is conducted for several reasons. The most common purpose is to
prevent
electromagnetic interference (EMI) from affecting sensitive electronics.
Aircraft lightning
protection has been demonstrated with conductive-particle-filled polymer
composites.
[0010] There are also certain polymers, e.g. polyaniline, polythiophene and
polypyrrole, which
could inherently conduct electricity, but they're often unstable conductors
(sensitive to oxygen and
moisture exposure), have low conductivity rates and are difficult to process.
[0011] Thermally Conductive Plastics
[0012] Plastics' thermal insulation, although beneficial in certain
applications, limits the utility
of plastics in many heat generating applications, because such insulation
causes undesirable
effects, such as hot spots and increased device temperature. Thermally
conductive plastics, or so-
called plastics with thermal management capability, are engineered to combine
the heat transfer
and cooling capabilities of metals with the design freedom, weight reduction
and cost advantages
of thermoplastic materials. Imparting thermal conductivity to plastics by
adding fillers changes the
way a plastic part responds to applied heat, because heat management is
critical to the performance,
lifetime, and reliability of electronic devices. A "good" thermally conductive
plastic material
manages the thermal energy rather than merely survive the applied thermal
energy.
[0013] Applications where thermally conductive plastic parts will be useful
include numerous
thermal management applications, such as heat sinks and other heat-removal
parts such as in
applications where there is heat build-up in electronics, appliances, lighting
(e.g. LED lights),
automotive products, and many other industrial products. Sensors' plastic
housings require
conductive plastics. For instance, with temperature sensors, thermally
conductive plastic
encapsulation can help improve the response of the temperature sensor itself.
Thermally
conductive compounds are also used to encapsulate motors and motor bobbins. A
fuel pump uses
a thermally conductive plastic to help keep fuel flowing in sub-freezing
temperatures.
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[0014] Traditionally, aluminum has been the prime material for controlling
higher heat fluxes
in electronics. However, sometimes aluminum's high thermal conductivity cannot
be effectively
utilized, such as in instances where it conducts heat to the surface of a
product faster than the air-
flow convection can remove the heat from the surface. Heat transfer in many
applications is
convection-limited, not conduction-limited (e.g. material-dependent).
Thermally conductive
plastics could provide heat transfer equivalent to some metal designs. Usually
for many
applications where convection is the limiting factor, the thermally conductive
plastics are a better
fit than metals.
[0015] Furthermore, thermally conductive plastics typically have lower
coefficients of thermal
expansion (CTE) than metals and can thereby reduce stresses due to
differential expansion; in fact,
the plastics more closely match those of silicon or ceramics.
[0016] Conductive Plastics Compounding Challenges
[0017] There are some technical challenges associated with compounding and
modifying
plastics to improve their thermal and/or electrical conductivity. High initial
cost is one of the
biggest obstacles to wider acceptance of conductive plastic formulations. A
key factor is high-
priced fillers used to achieve good electrical and/or heat conduction, which
result in conductive
plastic formulations which cost much more than metals. Furthermore, creating
conductive plastic
materials is not a simple step of mixing the conductive fillers into the
polymer matrix. Good
dispersion and formation of a conductive network throughout the polymer is
often required, which
network would serve as a pathway for passing the electrical charges and/or the
heat. Otherwise,
if the conductive particles are not dispersed well throughout the insulating
polymer medium, but
form isolated aggregates, then the final composite will not be conductive at
all; it will be a
composite of conductive particles trapped into (or coated with) an insulating
polymer.
[0018] To date, known mixing methods involve adding conductive particles
usually in a
molten state of the polymer, i.e. at temperatures above the melting point of
the material, Tm, which
requires energy to heat the polymer material above its Tm. And yet, many of
these mixing methods
result in aggregates of conductive particles or require high loading levels of
conductive fillers to
reach the required conductivity values.
[0019] Moreover, in order to ensure a high degree of electrical and/or
thermal conductivity, a
high concentration of conductive fillers is required, which might negatively
affect other properties
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of the base polymer (e.g. processability, mechanical properties). Higher
conductive filler content
could yield a good conductive composition (under assumption that the filler is
well-dispersed), but
this content usually has a negative influence on the mechanical properties and
processability of the
base polymer (due to the considerable increase in melt viscosity). Therefore,
for each material
type, a compromise has to be made regarding the amount of the filler and
desired properties.
[0020] Using nano-sized conductive particles vs. micron-sized conductive
particles might
solve the problem of high loading levels of conductive fillers. In general,
the concentration at
which the polymer composition becomes conductive is much lower, sometime an
order of
magnitude lower for compositions using nano-size conductive fillers compared
to the
compositions using micron-size conductive fillers. For instance, the
percolation zone, i.e. the
transition from insulating into conductive material, for a particular polymer
might occur at 10-20
vol% micron-size conductive filler or at 0.5-1 vol% if the same conductive
filler is used in
nanometer-sized particles, under the assumption that good dispersion is
achieved in both cases. Of
course, the filler loading level is further affected by the morphology,
particle shape and aspect
ratio in the case of anisotropic filler particles.
[0021] Taking into account the above-mentioned challenges of creating a
good dispersion of
conductive fillers in a polymer matrix which results in a conductive polymer
composition with a
satisfactory electrical and/or thermal conductivity values, there is a need
for a cost-efficient and
mixing-effective method for formulating conductive polymer-based compositions
and their
deposition as conductive coatings and conductive parts.
[0022] Plastics Recycling
[0023] Plastics recycling is the process of recovering different types of
plastic material in order
to reprocess them into various other products, usually downsized products. The
recycling of
plastics helps save energy and natural resources that are required to make
virgin plastics. In fact,
90 % of plastics are made from non-renewable fossil fuels. By recycling the
plastic waste, the
waste will not be accumulated in landfills, occupying land and releasing toxic
gases along with
other types of waste. Most of this plastic waste that potentially could be
recycled will end up in
the oceans and landfills, in addition to the plastics that can't be recycled.
The United Nations calls
the plastic pollution in the oceans a "planetary crisis". Another study
estimates the amount of
plastics in the oceans would outnumber the fish (by weight) by 2050. Moreover,
in the coming
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years, the plastics production is not going to slow down - it is expected to
double in the next 20
years and nearly quadruple by 2050.
[0024] Plastics waste is becoming a big problem, but only 9 % of plastics
waste is recycled.
There are many reasons for this, such as the technical hurdles required before
recycling. The waste
needs to go through several stages, e.g. sorting, washing, shredding,
classification, and then,
extruding or molding into a new product, usually a downsized product. Sorting
is a time-
consuming process required to separate different types of plastics, because
only plastics of the
same or similar properties can be recycled together and there are so many
different varieties of
plastics materials, many of which are made to be very durable and inert in the
environment.
Moreover, plastics can be only recycled a limited number of times before
ending up in a landfill.
Sometimes, the prices for recyclable plastic materials are higher than those
of virgin plastics,
because of lower oil prices, reduced demand for recycled plastics and their
limited applications.
Consequently, many of the plastic recycling companies are shutting down and
there is limited
interest in developing new technologies for plastics recycling.
[0025] The two main recycling methods for plastics are mechanical and
chemical plastics
recycling. Mechanical recycling is when the plastic is cut down into smaller
pieces, washed, melted
and remolded into a new product. Chemical recycling breaks the plastics' bonds
at the molecular
level. Each plastic material has characteristic bonds and specific catalysts
(chemicals) are used to
attack these particular bonds. Ideally, the plastic is broken down to a
monomer level (the catalyst
causes depolymerization), which monomers can then be used to make the same
fresh or so called
"virgin" plastic. However, chemical recycling usually requires very high
temperatures and yields
a mixture of multiple products that would need to be separated, another
tedious and expensive
process.
[0026] Therefore, there is a need for inexpensive technology that overcomes
the above-
mentioned challenges of plastics recycling and is capable of recycling a
variety of plastic materials
in a quick way without going through sorting and other tedious stages before
recycling.
SUMMARY OF THE INVENTION
[0027] Embodiments of this disclosure are directed to cost-effective
fabrication of conductive
plastic compositions, conductive coatings, e.g. EMI shielding, anti-static
(AS) and ESD coatings,
and 3D-conductive plastic objects with the aid of solid-state additive
manufacturing technology.
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Methods for in situ mixing of conductive fillers into thermoplastic polymer
material and its
subsequent deposition are disclosed. In addition, embodiments are directed to
methods for
recycling plastics waste by in situ shredding, mixing and subsequent
deposition into 3D parts and
coatings. Embodiments include any product produced by the disclosed methods.
[0028] Embodiments of the disclosure include, but are not limited to the
following:
[0029] Embodiment 1 is a method comprising: forming a conductive polymer or
plastic
composition with at least one conductive filler and at least one polymer or
plastic using solid-state
additive manufacturing; and forming a conductive 3D object by depositing the
conductive polymer
or plastic composition as a conductive coating or layer in a multi-component
part. Such methods
include a method of forming a conductive polymer or plastic composition with
at least one
conductive filler and at least one polymer or plastic through a solid-state
additive manufacturing
process; wherein the solid-state additive manufacturing process includes:
feeding the at least one
conductive filler and the at least one polymer or plastic through a hollow
spindle or tool of a solid-
state additive manufacturing machine; depositing the at least one conductive
filler onto or with the
at least one polymer or plastic; and generating severe plastic deformation of
the at least one
conductive filler and the at least one polymer or plastic by applying normal,
shear and/or frictional
forces by way of a rotating shoulder of the hollow tool such that the at least
one conductive filler
and/or the at least one polymer or plastic are in a malleable and/or visco-
elastic state in an interface
region, thereby producing the formed conductive polymer or plastic
composition.
[0030] Embodiment 2 is the method of Embodiment 1, wherein the conductive
polymer or
plastic composition comprises a conductive coating, conductive layer or
conductive 3D object.
[0031] Embodiment 3 is the method of Embodiment 1 or Embodiment 2, wherein
the
conductive polymer or plastic composition is a thermally conductive but
electrically insulating
composition.
[0032] Embodiment 4 is the method of any one of Embodiments 1-3, wherein
the conductive
polymer or plastic composition is an electrically conductive but thermally
insulating composition.
[0033] Embodiment 5 is the method of any one of Embodiments 1-4, wherein
the conductive
polymer or plastic composition is a thermally- and electrically- conductive
composition.
[0034] Embodiment 6 is the method of any one of Embodiments 1-5, wherein
the conductive
polymer or plastic composition is deposited on a non-conductive substrate or
object.
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[0035] Embodiment 7 is the method of any one of Embodiments 1-6, wherein
the conductive
polymer or plastic composition is deposited on a conductive substrate or
object.
[0036] Embodiment 8 is the method of any one of Embodiments 1-7, wherein
the conductive
polymer or plastic composition is deposited to form an anti-static (AS)
coating.
[0037] Embodiment 9 is the method of any one of Embodiments 1-8, wherein
the conductive
polymer or plastic composition is deposited to form an electrostatic discharge
(ESD) coating.
[0038] Embodiment 10 is the method of any one of Embodiments 1-9, wherein
the conductive
polymer or plastic composition is deposited to form an electromagnetic
interference (EMI)
shielding coating.
[0039] Embodiment 11 is the method of any one of Embodiments 1-10, wherein
the
conductivity of the plastic composition is higher than 102 S/cm.
[0040] Embodiment 12 is the method of any one of Embodiments 1-11, wherein
the
conductivity of the plastic composition is higher than 1 S/cm.
[0041] Embodiment 13 is the method of any one of Embodiments 1-12, wherein
the
conductive polymer or plastic composition is deposited to form a coating or
object with good heat
management properties.
[0042] Embodiment 14 is the method of any one of Embodiments 1-13, wherein
the thermal
conductivity of the plastic composition is higher than 1 W/mK.
[0043] Embodiment 15 is the method of any one of Embodiments 1-14, wherein
the thermal
conductivity of the plastic composition is higher than 10 W/mK.
[0044] Embodiment 16 is the method of any one of Embodiments 1-15, wherein
the
conductive polymer or plastic composition comprises micron-size conductive
fillers.
[0045] Embodiment 17 is the method of any one of Embodiments 1-16, wherein
the
conductive polymer or plastic composition comprises nano-size conductive
fillers.
[0046] Embodiment 18 is the method of any one of Embodiments 1-17, wherein
the
conductive polymer or plastic composition and/or conductive filler comprises
carbon nanotubes
(CNT).
[0047] Embodiment 19 is the method of any one of Embodiments 1-18, wherein
the
conductive polymer or plastic composition and/or conductive filler comprises
carbon black.
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[0048] Embodiment 20 is the method of any one of Embodiments 1-19, wherein
the
conductive polymer or plastic composition and/or conductive filler comprises
graphite.
[0049] Embodiment 21 is the method of any one of Embodiments 1-20, wherein
the
conductive polymer or plastic composition and/or conductive filler comprises
graphene.
[0050] Embodiment 22 is the method of any one of Embodiments 1-21, wherein
the
conductive polymer or plastic composition and/or conductive filler comprises
BN.
[0051] Embodiment 23 is the method of any one of Embodiments 1-22, wherein
the
conductive polymer or plastic composition and/or conductive filler comprises
A1203.
[0052] Embodiment 24 is the method of any one of Embodiments 1-23, wherein
the
conductive polymer or plastic composition and/or conductive filler comprises
AN.
[0053] Embodiment 25 is the method of any one of Embodiments 1-24, wherein
the
conductive polymer or plastic composition and/or conductive filler comprises
chopped steel fibers.
[0054] Embodiment 26 is the method of any one of Embodiments 1-25, wherein
the
conductive polymer or plastic composition and/or conductive filler comprises
chopped copper
fibers.
[0055] Embodiment 27 is the method of any one of Embodiments 1-26, wherein
the
conductive polymer or plastic composition and/or conductive filler comprises
metal particles.
[0056] Embodiment 28 is the method of any one of Embodiments 1-27, wherein
the
conductive polymer or plastic composition and/or conductive filler comprises
metal oxide
particles.
[0057] Embodiment 29 is the method of any one of Embodiments 1-28, wherein
the
conductive polymer or plastic composition and/or conductive filler comprises
two or more
different types of conductive fillers.
[0058] Embodiment 30 is the method of any one of Embodiments 1-29, wherein
the
conductive polymer or plastic composition has a coefficient of thermal
expansion (CTE) of less
than 5 x 106/ C.
[0059] Embodiment 31 is the method of any one of Embodiments 1-30, wherein
during
deposition the at least one conductive filler forms a 3D network within the
conductive polymer or
plastic composition.
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[0060] Embodiment 32 is the method of any one of Embodiments 1-31, wherein
one or more
solid-state additive manufacturing process parameters are adjusted so that the
at least one
conductive filler forms a 3D network within the conductive polymer or plastic
composition.
[0061] Embodiment 33 is the method of any one of Embodiments 1-32, wherein
the one or
more solid-state additive manufacturing process parameters comprise filler
material temperature,
spindle temperature, tool temperature, tool position, down force, tool
pressure, spindle torque,
spindle angular velocity, tool torque, tool transverse velocity, tool angular
velocity, filler material
flow rate, gas flow rate, and vibration.
[0062] Embodiment 34 is the method of any one of Embodiments 1-33, wherein
the at least
one conductive filler is a semiconductor.
[0063] Embodiment 35 is the method of any one of Embodiments 1-34, wherein
the at least
one conductive filler is ceramic.
[0064] Embodiment 36 is the method of any one of Embodiments 1-35, wherein
the at least
one polymer or plastic comprises reactive monomers.
[0065] Embodiment 37 is the method of any one of Embodiments 1-36, wherein
during the
deposition step the reactive monomers are cross-linked with the aid of light
and/or heat.
[0066] Embodiment 38 is a plastics recycling method comprising: providing
one or more
plastic waste as a first material; and processing the one or more plastic
waste material using a
solid-state additive manufacturing machine by adjusting one or more process
parameters in a
manner which transforms the one or more plastic waste into one or more 3D
printed layers or
objects. Such methods include a method of recycling plastic waste with a solid-
state additive
manufacturing machine, which method includes: providing a first material
comprising plastic
waste into the solid-state additive manufacturing machine; adjusting one or
more solid-state
additive manufacturing process parameters in a manner which incorporates the
plastic waste into
a 3D printed layer or object resulting from the solid-state additive
manufacturing process; wherein
the solid-state additive manufacturing process includes: feeding the first
material through a hollow
spindle or tool of the solid-state additive manufacturing machine; depositing
the first material onto
a second material, wherein the first material is below its melting point (Tm)
during deposition; and
generating severe plastic deformation of the first material by applying
normal, shear and/or
frictional forces by way of a rotating shoulder of the hollow tool such that
the first and second
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material are in a malleable and/or visco-elastic state in an interface region,
thereby producing the
resultant solid-state additive manufacturing 3D printed layer or object with
the incorporated
plastic waste.
[0067] Embodiment 39 is the method of Embodiment 38, wherein one or more of
the solid-
state additive manufacturing process parameters are adjusted in a manner to
cause severe plastic
deformation of the first material by applying normal, shear and/or frictional
forces.
[0068] Embodiment 40 is the method of Embodiment 38 or Embodiment 39,
wherein the solid-
state additive manufacturing process causes a malleable state in the surface
region of the second
material on which the deformed first material is deposited onto by way of a
rotating shoulder of
the hollow tool.
[0069] Embodiment 41 is the method of any one of Embodiments 38-40, further
comprising
deposition of one or more layers of the first material onto the second
material.
[0070] Embodiment 42 is the method of any one of Embodiments 38-41, wherein
the first
material comprises a mixture of plastic waste and virgin plastics and is
provided as a single
feedstock.
[0071] Embodiment 43 is the method of any one of Embodiments 38-42, wherein
the first
material comprises plastic waste and virgin plastic material which are
provided as separate
feedstocks.
[0072] Embodiment 44 is the method of any one of Embodiments 38-43, wherein
the first
material comprises a mixture of plastics waste and metals provided as a single
feedstock.
[0073] Embodiment 45 is the method of any one of Embodiments 38-44, wherein
the first
material comprises plastic waste and metal materials provided as separate
feedstocks.
[0074] Embodiment 46 is the method of any one of Embodiments 38-45, wherein
the first
material comprises a mixture of plastics waste and ceramics provided as a
single feedstock.
[0075] Embodiment 47 is the method of any one of Embodiments 38-46, wherein
the first
material comprises a plastic waste and ceramic materials provided as separate
feedstocks.
[0076] Embodiment 48 is the method of any one of Embodiments 38-47, wherein
the first
material comprises a mixture of plastics waste and reinforcing particles.
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[0077] Embodiment 49 is the method of any one of Embodiments 38-48, wherein
the first
material comprises a mixture of plastics waste and reinforcing fibers.
[0078] Embodiment 50 is the method of any one of Embodiments 38-49, wherein
the first
material comprises a mixture of plastics waste and chopped reinforcing fibers.
[0079] Embodiment 51 is the method of any one of Embodiments 38-50, wherein
the first
material comprises a mixture of plastics waste and a lubricant.
[0080] Embodiment 52 is the method of any one of Embodiments 38-51, wherein
the first
material comprises a mixture of plastics waste and micro-particles.
[0081] Embodiment 53 is the method of any one of Embodiments 38-52, wherein
the first
material comprises a mixture of plastics waste and nano-particles.
[0082] Embodiment 54 is the method of any one of Embodiments 38-53, further
comprising
supplying a gas during deposition of the first material to form a porous
deposit.
[0083] Embodiment 55 is the method of any one of Embodiments 38-54, wherein
the first
material comprises a first batch comprising plastic waste and a second batch
comprising virgin
plastics, resulting in deposition of alternate layers of waste and virgin
plastics.
[0084] Embodiment 56 is the method of any one of Embodiments 38-55, wherein
the first
material comprises a first batch comprising plastic waste and a second batch
comprising metals,
resulting in deposition of alternate layers of waste plastics and metal.
[0085] Embodiment 57 is the method of any one of Embodiments 38-56, wherein
the first
material comprises a first batch of plastic waste and a second batch of
ceramics, resulting in
deposition of alternate layers of waste plastics and ceramics.
[0086] Embodiment 58 is the method of any one of Embodiments 38-57, wherein
the first
material comprises plastic waste and virgin plastics as feed materials that
are gradually changing
from around 0 % by volume plastic waste to around 100 % by volume plastic
waste, or from around
0 % by volume virgin plastics to around 100 % by volume virgin plastics.
[0087] Embodiment 59 is the method of any one of Embodiments 38-58, wherein
the first
material comprises plastic waste in the form of plastic granules, beads,
pellets, powder or irregular
pieces produced by shredding used plastic objects, such as plastic bottles,
plastic bags, and/or
plastic cups.
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[0088] Embodiment 60 is the method of any one of Embodiments 38-59, further
comprising
shredding used plastic objects into smaller pieces to provide the plastic
waste for the first material.
[0089] Embodiment 61 is the method of any one of Embodiments 38-60, wherein
the second
material comprises plastic such that the first material comprising the plastic
waste is deposited
onto a plastic substrate.
[0090] Embodiment 62 is the method of any one of Embodiments 38-61. wherein
the second
material comprises metal such that the first material comprising the plastic
waste is depositing
onto a metal substrate.
[0091] Embodiment 63 is the method of any one of Embodiments 38-62, wherein
the second
material comprises ceramic such that the first material comprising the plastic
waste is deposited
onto a ceramic substrate.
[0092] Embodiment 64 is the method of any one of Embodiments 38-63, wherein
the resultant
solid-state additive manufacturing 3D printed layer or object with the
incorporated plastic waste
is a 3D object.
[0093] Embodiment 65 is the method of any one of Embodiments 38-64, wherein
the resultant
solid-state additive manufacturing 3D printed layer or object with the
incorporated plastic waste
is a surface coating.
[0094] Embodiment 66 is the method of any one of Embodiments 38-65, wherein
the resultant
solid-state additive manufacturing 3D printed layer or object with the
incorporated plastic waste
is a plastic block.
[0095] Embodiment 67 is the method of any one of Embodiments 38-66, wherein
the one or
more solid-state additive manufacturing process parameters comprise one or
more of filler material
temperature, spindle temperature, tool temperature, tool position, downward
force, tool pressure,
spindle torque, spindle angular velocity, tool torque, tool transverse
velocity, tool angular velocity,
filler material flow rate, gas flow rate, and/or vibration.
[0096] Embodiment 68 is the method of any one of Embodiments 38-67, wherein
the plastic
waste comprises one or more of the following plastics: PET (Polyethylene
Terephthalate), HDPE
(High-Density Polyethylene), PVC (Polyvinyl Chloride), LDPE (Low-Density
Polyethylene), PP
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(Polypropylene), PS (Polystyrene), Other plastics, such as Acrylic, Nylon,
Polycarbonate and
Polylactic acid (PLA).
[0097] Embodiment 69 is a 3D printed layer, object, or product produced by
the method of
any one of Embodiments 38-68.
[0098] Embodiment 70 is the 3D printed layer, object, or product of
Embodiment 69, wherein
the plastic waste or recycled plastic comprises one or more of the following
plastics: PET
(Polyethylene Terephthalate), HDPE (High-Density Polyethylene), PVC (Polyvinyl
Chloride),
LDPE (Low-Density Polyethylene), PP (Polypropylene), PS (Polystyrene), Other
plastics, such as
Acrylic, Nylon, Polycarbonate and Polylactic acid (PLA).
[0099] Embodiment 71 is the 3D printed layer, object, or product of
Embodiment 69 or
Embodiment 70, wherein the plastic waste or recycled plastic comprises rigid
plastic.
[0100] Embodiment 72 is the 3D printed layer, object, or product of any one
of Embodiments
69-71, which is or is a component of a plastic pipe, plastic tile, or plastic
block.
[0101] Embodiment 73 is a 3D printed object comprising a first layer
adjacent to a second
layer, which first layer comprises plastic waste or recycled plastic and which
second layer
comprises virgin plastic.
[0102] Embodiment 74 is a 3D printed object comprising a first layer
adjacent to a second
layer, which first layer comprises plastic waste or recycled plastic and which
second layer
comprises no plastic.
[0103] Embodiment 75 is the 3D printed object of Embodiment 74, wherein the
second layer
comprises metal.
[0104] Embodiment 76 is the 3D printed object of Embodiment 74, wherein the
second layer
comprises ceramic.
[0105] Embodiment 77 is the 3D printed object of Embodiment 74, wherein the
second layer
comprises both metal and ceramic.
[0106] Embodiment 78 is a 3D printed object comprising a first layer
adjacent to a second
layer, which first layer comprises a first waste plastic and which second
layer comprises a second
waste plastic which is different from the waste plastic of the first layer.
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[0107] Embodiment 79 is the 3D printed object of Embodiment 78, which first
waste plastic
and second waste plastic are selected from the following plastics: PET
(Polyethylene
Terephthalate), HDPE (High-Density Polyethylene), PVC (Polyvinyl Chloride),
LDPE (Low-
Density Polyethylene), PP (Polypropylene), PS (Polystyrene), Other plastics,
such as Acrylic,
Nylon, Polycarbonate and Polylactic acid (PLA).
[0108] Embodiment 80 is the 3D printed object of Embodiment 78 or
Embodiment 79, which
is a plastic pipe, plastic tile, or plastic block.
[0109] These and other Embodiments will be elaborated upon in the foregoing
Detailed
Description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0110] The accompanying drawings illustrate certain aspects of embodiments
of the present
invention, and should not be used to limit the invention. Together with the
written description the
drawings serve to explain certain principles of the invention.
[0111] FIG. 1 is a diagram providing electrical conductivity values for
insulating,
semiconducting and conductive materials, where the electrically conductive
polymer compositions
are made by different methods (other than by solid-state additive
manufacturing) of dispersion of
conductive fillers in a polymer matrix.
[0112] FIGS. 2A and 2B are schematic diagrams of a solid-state additive
manufacturing
system capable of in situ compounding and deposition of conductive plastic
layers and coatings
over exiting parts according to embodiments.
[0113] FIGS. 3A-3H are schematic illustrations of potential examples of
formation of
insulating and "conductive" networks according to embodiments. The examples
include: particle-
type conductive fillers at low loading level not sufficient to form a 3D
conductive network
(FIG. 3A) and at higher loading level sufficient to form a 3D conductive
network (FIG. 3B), as
well as particle-type fillers forming isolated aggregates that do not yield a
conductive 3D network
(FIG. 3C). Needle-like or rod-like conductive fillers at low loading levels
yielding insulating
material (FIG. 3D) and at higher loading levels yielding a conductive network
(FIGS. 3E and 3F)
are provided as well. Examples of chopped fiber-type fillers at low loading
levels and higher
loading levels, resulting in insulating and conductive materials,
respectively, are provided in
FIGS. 3G and 3H.
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[0114] FIG. 4 is a schematic diagram of a solid-state additive
manufacturing system capable
of accepting and shredding various types of plastics waste and its subsequent
deposition according
to an embodiment.
[0115] FIG. 5A is a schematic illustration of a solid-state additive
manufacturing-deposited
plastic waste layer on a substrate according to an embodiment, while FIG. 5B
is a schematic
illustration of solid-state additive manufacturing deposition of two different
layers from two
different plastic waste feedstocks according to an embodiment. FIG. 5C is a
schematic illustration
of a solid-state additive manufacturing deposition of a layer from a feedstock
comprising virgin
and waste plastics according to an embodiment. FIG. 5D is a schematic
illustration of a solid-state
additive manufacturing generated compositional gradient along the
translational direction using
virgin and waste plastic as feedstock according to an embodiment, while FIG.
5E is a schematic
illustration of a solid-state additive manufacturing-generated compositional
gradient along the
thickness of deposited layers using virgin and waste plastic feedstocks at
different ratios according
to an embodiment. FIG. 5F is a schematic illustration of alternating solid-
state additive
manufacturing-deposited layers comprising recycled plastic layers and other
type of layers,
e.g. virgin plastic layer according to an embodiment.
[0116] FIG. 6A is a schematic illustration showing phase separation between
two plastics X
and Y exhibiting phase boundaries between the two phases, which are usually
structurally weak
zones, according to an embodiment.
[0117] FIG. 6B is a schematic illustration showing no phase boundaries in
the polymer system
comprising different phases as a result of using a compatibilizer according to
an embodiment.
[0118] FIG. 7A is a schematic illustration of cross-sections of solid-state
additive
manufacturing-deposited layers of virgin plastic (VP) and recycled waste
plastic (WP) using inter-
locks according to embodiments. FIG. 7B is a schematic illustration of cross-
sections of different
interlocks according to embodiments.
DETAILED DESCRIPTION OF VARIOUS EMBODIMENTS OF THE INVENTION
[0119] Reference will now be made in detail to various exemplary
embodiments of the
invention. It is to be understood that the following discussion of exemplary
embodiments is not
intended as a limitation on the invention. Rather, the following discussion is
provided to give the
reader a more detailed understanding of certain aspects and features of the
invention.
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[0120] As used herein, the term "solid-state additive manufacturing" refers
to and is
interchangeable with "additive friction stir" and/or any process described
herein, such as
manufacturing processes using a rotatable and/or translatable tool that
delivers feedstock through
the tool and processes the feedstock and/or substrate in a manner to deform
one or both of the
feedstock and/or substrate, in whole or part, to allow for joining of the
feedstock and substrate
and/or one or more additional structural feature.
[0121] As used herein, the term "coating material" is used interchangeably
with "filler
material" and/or "feedstock" and/or "consumable" and/or "consumable material,"
which each
independently or collectively relate to an additive material which is fed
through a throat of a
rotating stirring tool as described in this disclosure.
[0122] Solid-state additive manufacturing technology offers a possibility
for in situ mixing
and dispersion of conductive filler particles in a thermoplastic matrix
without melting the matrix,
while rendering the resulting product electrically and/or thermally
conductive. A diagram
providing electrical conductivity values for insulating, semiconducting and
conductive materials,
where the electrically conductive polymer compositions are made by different
methods (other than
by solid-state additive manufacturing) of dispersion of conductive fillers in
a polymer matrix is
provided in FIG. 1.
[0123] Solid-state additive manufacturing technology is an environmentally
friendly
technology operating in an open atmosphere without melting the material. The
solid-state additive
manufacturing system deposits the material by thermo-mechanical means: the
system causes a
severe plastic deformation in the material due to a combination of different
forces and rotation to
make both the deposited material and the material being deposited onto
malleable. The materials
are in a solid state ¨ a unique distinction from competing technologies. Due
to the friction stirring
action, individual grains/particles/pieces are broken up into smaller sizes
and consolidated. The
entire operation occurs in air making the solid-state additive manufacturing
system less complex
and less expensive to operate. After the solid-state additive manufacturing
process is completed,
there is no need for the additional steps required by competing melt-based
processes, such as
annealing or sintering.
[0124] The thermoplastic polymer being processed in the solid-state
additive manufacturing
process is in a visco-elastic state, i.e. at temperatures above the glass
transition temperature of the
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material, Tg, but still below its melting point, Tm, which is a main
distinction from all the other
known methods for particle dispersion in polymeric materials. This also means
solid-state additive
manufacturing processes have lower energy costs in comparison to other known
processes, as there
is no need for energy to melt the material. The addition of conductive fillers
and their dispersion
in the polymer are facilitated by intense forces, friction forces and other
types of forces generated
within the solid-state additive manufacturing system, which forces reduce the
viscosity of the
polymer, which is not in a molten state. Furthermore, the solid-state additive
manufacturing system
is capable of simultaneously depositing the in situ generated conductive
compositions into desired
3D objects, layers and/or coatings.
[0125] Solid-state additive manufacturing technology is capable of in situ
shredding, mixing
and consolidating different plastic materials and subsequent printing into
desirable 3D shapes or
coatings. Thus, solid-state additive manufacturing technology is an
inexpensive way of processing
a variety of used plastic materials and plastic objects without the need for
the preliminary stages
required in the conventional plastic recycling industry.
[0126] In some aspects, the addition of conductive particles to a polymer
material (or a plastic
formulation) contribute to improvement of both the electrical and thermal
conductivities of the
base polymeric material. In other aspects, the added conductive particles
yield improvement in the
electrical conductivity of the matrix material, and yet in another aspects,
the conductive additives
increase the thermal conductivity only. FIG. 2A is a schematic presentation of
a solid-state additive
manufacturing system capable of in situ compounding of a conductive plastic
formulation and its
subsequent deposition. The system comprises a feeding section (hopper) 202A,
where the
feedstock 201 (or multiple feedstock streams 201A, 201B, 201C) enter the solid-
state additive
manufacturing system. The raw polymer or plastic formulation (201A) used as a
feedstock in the
solid-state additive manufacturing system is a virgin polymer or used
(recycled) plastic supplied
in, without limitation, any of the following forms: granules, powder, pellets,
wires, bars, sheets
and/or their combination. The conductive fillers are also supplied as a
continuous or discontinuous
feeding stream, e.g. 201B into the system. When needed, a variety of other
additives, e.g.
surfactants, stabilizers and so on (201C), are added to enable good dispersion
and miscibility
between the polymer matrix and conductive particles. The feedstock then goes
through the spindle
202B of the solid-state additive manufacturing system, where the feedstock is
transformed into a
malleable state, and then is deposited on the substrate via a hollow tool
202C. Additional solid-
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state additive manufacturing system elements might include inert gas supply
202D, for cases where
the material deposition is sensitive to air/oxygen, and a light source or heat
source 202E, for cases
where external energy supplied as ultraviolet (UV), visible or infrared (IR)
light aids in the
deposition of the conductive composition 203A.
[0127] In some embodiments, the compounded conductive composition 203A is
deposited in
multiple layers 203B, 203C and 203D to build a 3D structure or part (FIG. 2A).
In other
embodiments, the compounded conductive composition 203A is deposited as a
conductive coating
or a conductive layer 203B on top of an existing substrate, structure, or part
204 (FIG. 2B).
[0128] In some embodiments, by adjusting the solid-state additive
manufacturing process
parameters, such as the feeding rate, spindle and tool rotation, spindle and
tool temperature, and
torque, the solid-state additive manufacturing system provides a good
dispersion of the conductive
fillers and formation of a conductive 3D percolation network throughout the
polymer (plastic
material). The solid-state additive manufacturing process conditions are
easily adjustable and
controlled depending on the type of polymer matrix, its glass transition
temperature (Tg) and
melting temperature (T.,), friction coefficient and compression strength,
among the other polymer
properties. Examples include adding conductive particle-type fillers (FIGS.
3A, 3B and 3C), where
a critical filler amount is needed to form a continued network of conductive
particles (FIG. 3B),
and thus, formation of a conductive material composition. At low loading
levels, even at good
dispersion process conditions, there is no formation of a continuous network
in 3D space (FIG.
3A). When the solid-state additive manufacturing process conditions are not
adjusted for the
particular material type and the filler type, then the final composition will
be an insulating material
comprising clumps (aggregates) of the filler particles in an insulating medium
(FIG. 3C).
[0129] Other examples include dispersing conductive needle-like or rod-like
fillers in
insulating plastic materials (FIGS. 3D, 3E and 3F). At low loading levels,
there is no 3D network
formation of conductive fillers, and thus, the result is an insulating
composite material (FIG. 3D).
At higher loading levels, a 3D conductive network is formed depending on the
filler's aspect ratio
(FIGS. 3E and 3F). Higher aspect ratio fillers (FIG. 3F) will yield a 3D
network at a much lower
loading level than fillers with a smaller aspect ratio (FIG. 3E). In general,
the loading level for rod-
like fillers is usually much lower than the loading level of the particle type
filler to form a 3D
network within the same plastic material.
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[0130] In certain examples, chopped conductive fibers, e.g. steel, copper,
carbon fibers and
others, are used as conductive fillers (FIGS. 3G and 3H). Preparation of a
conductive composition
(FIG. 3H), which is highly dependent on the filler aspect ratio and the
loading level, is possible
with particular solid-state additive manufacturing processing conditions that
will give rise to high
"fluidity" of the composition without melting it. FIG. 3G is a schematic of an
insulating
composition where the loading level of conductive fibers is lower than the
critical level.
[0131] In some embodiments a combination of two or more fillers is used to
achieve the
required electrical conductivity and/or thermal conductivity value of the
final solid-state additive
manufacturing-processed composition. One example includes a mixture of
graphene sheets'
particles and spherical metal or metal oxide particles added to a plastic
matrix to achieve the
desired conductivity. Another example includes fiber-like or needle-like
fillers combined with
particle-type fillers to achieve the desired conductivity value at a much
lower filler loading level
than the levels needed if the individual fillers were used separately.
[0132] In certain aspects, polymer matrices, like polyamides (PAA), nylon 6
and 66 (Ny6,
Ny66), polyphenyl sulfone (PPS), polysulfone (PSU), polybutylene terephthalate
(PBT),
acrylonitrile-butadiene-styrene (ABS), polyetherimide (PEI), polyesters,
polycarbonate (PC),
polystyrene (PS), polyolefines (PP, LDPE, HDPE), polyvinylchloride (PVC) and
others are used
for solid-state additive fabrication of conductive plastic compositions,
conductive coatings and
conductive parts.
[0133] In other aspects, thermoplastic elastomers are supplied in the solid-
state additive
manufacturing system along with conductive fillers to make conductive
elastomeric compositions
and parts.
[0134] In some aspects, a solid-state additive manufacturing compounded
plastic formulation
comprising reactive species (monomers) is additionally cross-linked with the
aid of UV light or
heat 202E during the solid-state additive manufacturing deposition step (FIG.
2A).
[0135] In certain embodiments, the plastic material is added in the solid-
state additive
manufacturing feeding system together with chopped steel fibers or steel
powder to produce an
EM shielding composition and its subsequent deposition over parts and surfaces
that need EM
shielding functionality. In the case of steel fiber filler, a high shielding
effectiveness at lower
loading level is possible in comparison to that obtained with powder or
particle-filled plastic.
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[0136] In other embodiments, single-walled and multi-walled carbon
nanotubes (SW- and
MW-CNT), carbon black, or other types of metal fibers or particles are added
to a plastic material
to make effective EMI shielding coatings or part-building layers.
[0137] In some embodiments, a plastic material in the solid-state additive
manufacturing
feeding system is blended together with chopped copper wire or copper
powder/particles resulting
in an electrically- and thermally- conductive plastic composition.
[0138] In some embodiments, solid-state additive manufacturing - compounded
conductive
thermoplastic compositions provide anti-static (AS) protection or protection
from electrostatic
discharge (ESD).
[0139] In certain aspects, electrically- and/or thermally- conductive
fillers in the form of
flakes, platelets or chopped sheets are used. Particular examples include
thermally conductive, but
electrically insulating plastic compositions with a low coefficient of thermal
expansion and good
mechanical strength for use in electronic packaging manufactured by the solid-
state additive
manufacturing process using ceramic conductive particles. For instance,
ceramic particles such as
BN, 5i02, Si3N4, A1203, AN are used as conductive fillers in the solid-state
additive fabrication
of conductive plastics.
[0140] Solid-state additive manufacturing - compounded plastic formulations
enable heat to
be distributed evenly throughout the part and away from the heat source.
Unlike traditional metals,
which are good conductors but in many applications are limited by their
convection cooling, solid-
state additive manufacturing - compounded plastic compositions offer greater
efficiency, because
the convection rate and thermal conductivity rate are closely matched.
[0141] In certain embodiments, the electrical conductivity of the plastics
may be enhanced by
the addition of aluminum flakes, carbon fibers, carbon black powder, carbon
nanotubes, stainless
steel fibers, metal powder, and nickel-coated polymer fibers. In yet another
example, graphene or
graphite is used to fabricate conductive plastics by solid-state additive
manufacturing technology.
[0142] In some embodiments, anisotropic conductive fillers with high aspect
ratio, e.g.
L/W>10, where L is the filler length and W is the filler width, are used in
the solid-state additive
manufacturing process. Lower filler loading levels (less than 10 vol%) are
required to make solid-
state additive manufacturing conductive plastic formulations than the
formulations made with
fillers of lower aspect ratio.
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[0143] Furthermore, it is known that the thermal and electrical
conductivity of filled plastic
compositions depends on filler loading, filler morphology, filler aspect ratio
and orientation (if
any) and the overall composition micro- and nano-structure. In certain
aspects, the solid-state
additive manufacturing system coupled with particular process conditions is
capable of uniquely
distributing and orienting the fillers (in case of anisotropic fillers) in a
low viscous plastic medium.
[0144] In some embodiments, graphite fibers or particles, which conduct
electricity, as well as
heat, are used in the solid-state additive manufacturing process of making
conductive plastics for
applications where Radio Frequency Interference (RFI) shielding is required,
such as hand-held
communication devices.
[0145] In other embodiments, ceramic additives which are heat-conductive,
but electrically-
insulative are added to the solid-state additive manufacturing - compounded
plastic composition.
Whereas common thermoplastics have a thermal conductivity of around 0.2 W/mK,
i.e. are thermal
insulators, certain examples of solid-state additive manufacturing -
compounded plastics could
have a conductivity in the range of 1-10 W/mK or even an order of magnitude
higher.
[0146] Some embodiments include solid-state additive manufacturing -
formulated plastic
compositions with electrical conductivity values above 10-2 S/cm, and
compositions with
conductivity above 1 S/cm.
[0147] Certain embodiments are related to solid-state additive fabrication
of plastics with
anisotropic conductive properties, which is achieved by using liquid
crystalline polymer (LCP)
matrix and/or anisotropic conductive fillers. During the solid-state additive
manufacturing
deposition step, the LCP molecules and/or fillers become oriented in the
deposited coatings or 3D
objects.
[0148] In certain embodiments, the solid-state additive manufacturing
feeding system is used
for recycling polymer (plastic) waste (FIG. 4). For this purpose, the feeding
section 402A
comprises a hopper, and very often, a shredder. The hopper and shredder are
designed to accept
and process a variety of plastic materials and shapes. The shredder is
designed to cut the plastics
into smaller pieces. The system further comprises a spindle 402B, a hollow
tool 402C, an inert gas
supplying unit 402D and external field unit 402E (e.g. UV light source, heat
source). The plastic
waste 401 used as feedstock can be mixed with virgin plastics and/or
additives, such as fillers,
compatibilizers, and stabilizers.
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[0149] In a specific embodiment, used plastic bottles usually made of
polyethylene
terephthalate (PET) serve as a feeding material in the solid-state additive
manufacturing system.
The bottle caps, usually made of a different plastic material, such as
polypropylene (PP) or
polyethylene (PE), do not need to be separated from the bottles, which is not
the case with other
plastics recycling technologies.
[0150] In another embodiment, used plastic bottles are mixed with other
plastic waste, e.g.
shopping plastic bags, in various ratios in the solid-state additive
manufacturing feeding system,
and processed together into 3D printed parts.
[0151] In some embodiments, polystyrene (PS) or polystyrene foam (e.g.
Styrofoam) or both
are used as a feeding material. In other embodiments, polyvinylchloride (PVC)
shredded objects
are used as feedstock in the solid-state additive manufacturing system.
[0152] According to embodiments, any or all of the following plastics,
listed according to their
standard Resin Identification Code (RIC) are used as feeding material:
[0153] #1 - PET (Polyethylene Terephthalate),
[0154] #2 - HDPE (High-Density Polyethylene),
[0155] #3 ¨ PVC (Polyvinyl Chloride),
[0156] #4 ¨ LDPE (Low-Density Polyethylene),
[0157] #5 ¨ PP (Polypropylene),
[0158] #6 ¨ PS (Polystyrene),
[0159] #7 ¨ Other plastics, such as Acrylic, Nylon, Polycarbonate and
Polylactic acid (PLA).
[0160] In embodiments, the feed of used plastics is turned into plastic
foam by the solid-state
additive manufacturing system. As an example, once the used plastic material
is cut into small
pieces, which are then severely deformed and consolidated, the material is
deposited with the aid
of a blown gas (N2). The final deposited layers are porous, including open or
closed pores or both
depending on the solid-state additive manufacturing process conditions. In
another example, two
types of plastics with very different melting points (Tm) are used as a
feedstock. During the solid-
state additive manufacturing process, one of the materials (with lower Tm)
decomposes into gases
that form pores enclosed within the other deposited material (with higher Tm).
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[0161] In some embodiments, the solid-state additive manufacturing -
deposited layer 503
resulting from a plastic waste feedstock in the solid-state additive
manufacturing system is
deposited on a substrate 504 made of plastic, ceramic or metallic material
(FIG. 5A).
[0162] In embodiments, a mixture of two or more different plastic waste
materials or shredded
plastic objects or their combination is used as a single feedstock in the
solid-state additive
manufacturing system, resulting in a recycled plastic layer made of different
plastic materials. In
other embodiments, different plastic waste materials are used as different
feedstocks in the solid-
state additive manufacturing machine and deposited as separate layers 503A and
503B (FIG. 5B).
[0163] In particular embodiments, the virgin plastic and recycled plastic
are mixed together in
the feeding section and deposited as a single layer 503C on a substrate 504
(FIG. 5C).
[0164] In embodiments, virgin plastics (VP) and waste plastics (WP) in
different volume
percentages, ranging from VP/WP 0/100 % by volume to around 100/0 % by volume,
are used as
feedstocks in the solid-state additive manufacturing system. VP and WP can be
mixed together
simultaneously in different ratios in the feeding section of the solid-state
additive manufacturing
machine before they are being deposited. In some embodiments VP and WP are the
same type of
plastics, while in other embodiments, they are be different types of plastics.
[0165] In some embodiments, the VP/WP ratio is varied in the feedstock
during the solid-state
additive manufacturing deposition process yielding gradient composition in the
solid-state additive
manufacturing printed object or solid-state additive manufacturing deposited
layers (FIGS. 5D and
5E). The compositional gradient can be achieved along the deposition direction
i.e. translational
direction in some embodiments (FIG. 5D), while in other embodiments, the
gradient forms along
the thickness of the deposited layers, 503B, 503C, 503D, 503E, 503F, 503G and
503H
corresponding to e.g. VP/WP = 0/100, 10/90, 30/70, 50/50, 70/30, 90/10 and
100/0, respectively,
as presented in FIG. 5E.
[0166] In some examples, the compositional gradient can be any variation in
terms of changing
VP/WP ratio or the plastics type (e.g. Plastic A/Plastic B ratio) along the
deposition direction or
along the thickness of the deposited layers. In other examples, the gradient
can be any variation in
changing plastic/ceramic or plastic/metal ratio.
[0167] In specific embodiments, VP and WP are used in the solid-state
additive manufacturing
process as separate feedstocks. For instance, the feedstock in the solid-state
additive manufacturing
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machine are alternating VP material and WP material, resulting in alternating
VP layer 503H and
WP layer 503B, respectively, as presented in FIG. 5F. In another embodiment,
the WP layers
alternate with metal interlayers and yet in another embodiment, the WP layers
alternate with
ceramic or metal interlayers. The thickness of all the involved layers can be
the same or different.
[0168] In some embodiments, besides the plastics feedstock, a lubricant, a
compatibilizer, a
plasticizer, a filler and/or any other additive is used in the solid-state
additive manufacturing
process. The additive helps improve blending and compatibilization of
different pieces or different
materials or could provide better flow characteristics in case of brittle
plastics. In yet another
embodiment, since used plastics are usually more brittle than virgin plastics
materials, non-
conventional low molecular weight compounds, e.g. oligomers, long-chain
molecules, elastomers
and so on, are used to provide a certain degree of elasticity and/or ductility
in the final deposited
layer/product.
[0169] In another embodiment, reinforcing particles or fibers are added to
the solid-state
additive manufacturing feedstock of used plastics. Reinforcing particles or
fibers can be selected,
without limitation, from the following categories: carbon fibers, glass
fibers, metal particles, metal
fibers, ceramic particles, and high-performance polymer fibers.
[0170] When different types of plastics are mixed and melted together, they
tend to phase-
separate, like oil and water, i.e. form different phases. The phase boundaries
separating different
phases in polymeric systems usually cause structural weakness in the resulting
material, which can
be used in limited applications (FIG. 6A). Examples include two most widely
used commodity
plastics, polypropylene and polyethylene, or Plastic X and Plastic Y, which
phase separate and
limit the ability for recycling and processing them together. In order to
avoid the issues of phase
separation, various chemicals, such as compatibilizers, have been proposed to
overcome the
difficulties associated with phase separation during recycling.
[0171] During the solid-state additive manufacturing processes, the
materials are not melted,
but are in a so-called malleable state below their melting point (I'm). The
problem of blending two
or more different plastic materials that need to be recycled together is
solved by adding a
compatibilizer (FIG. 6B). Usually, the compatibilizer is a block copolymer, in
which one block
(part) of the block copolymer is compatible (miscible) with one of the plastic
materials in the
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mixture, while the other block is compatible with the other plastic material.
The compatibilizer
can also be a graft copolymer or a head-tail molecule or a branched type
molecule.
[0172] In certain embodiments, the solid-state additive manufacturing
processed plastic waste
layer is added as a coating to an object or a substrate. In other embodiments,
the solid-state additive
manufacturing printed waste plastic layer is added as an "inexpensive filler"
layer between VP,
metallic or ceramic layers.
[0173] In some embodiments, the surface of the substrate and/or any of the
layers is treated to
improve the bonding to the adjacent layer. The treatment might include, but is
not limited to, any
of the following treatments or any combination of them: laser treatment,
plasma treatment, corona
treatment, chemical surface functionalization, etching, primer/adhesion
promoter use, and ion
bombardment.
[0174] In other embodiments, inter-locks 705A are created in one of the
layers to improve the
bonding between the layers, e.g. in the VP layer 703A that is bonded to the WP
layer 703B or vice
versa, both deposited by the solid-state additive manufacturing processes
(FIG. 7A). Dovetail-type
inter-locks 705B and other types of inter-locks 705C, 705D and 705E can also
be manufactured
(FIG. 7B).
[0175] In some embodiments, beside used plastic bottles, the solid-state
additive
manufacturing machine is capable of accepting and processing cups, caps, lids,
straws, food
wrappers, flexible packaging, foils, films, shopping bags and others, some of
them not recyclable
to date due to their low quantities or a chemical nature different than the
bulk plastics waste
generated.
[0176] In certain embodiments, a variety of products are manufactured by
solid-state additive
manufacturing processes. For instance, plastic pipes, plastic tiles (flooring
products), and other
products are processed from a plastic waste feedstock or a feedstock which
includes a certain
fraction of waste plastics. In other examples, plastic blocks are processed
from a plastic waste
feedstock, which are later shaped into desirable objects and shapes by other
processes or operations
known in the art.
[0177] In another embodiment, the substrate(s) and/or the filler material
include metal or
metallic materials. The filler material, or the substrate(s) can be
independently selected from any
metal, including for example Al, Ni, Cr, Cu, Co, Au, Ag, Mg, Cd, Pb, Pt, Ti,
Zn, or Fe, Nb, Ta,
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Mo, W, or an alloy comprising one or more of these metals. In embodiments, the
substrate(s)
and/or the filler material are polymeric material. Non-limiting examples of
polymeric materials
useful as a filler material include polyolefins, polyesters, nylons, vinyls,
polyvinyls, acrylics,
polyacrylics, polycarbonates, polystyrenes, polyurethanes, and the like.
[0178] In still yet another embodiment, the filler material is a composite
material comprising
at least one metallic material and at least one polymeric material. In other
embodiments, multiple
material combinations can be used for producing a composite at the interface.
[0179] In embodiments, the substrate(s) can be provided as a sheet or
plate, such as sheet metal
or metallic plates or plastic sheets or plates, in a variety of dimensions for
joining, including with
a width and/or length of from about 1 inch to about 20 feet, such as for
example 2'x2', 2'x3', 2'x4',
3'x4', 4'x4, 5'x5, 6'x4', and the like. The size of the sheets is highly
dependent on and can fit any
desired application. Depths of the substrate(s) as described above can be on
the order of
micrometers to centimeters.
[0180] In these solid-state additive manufacturing embodiments, the filler
material (for
example, solid bar or powder, and/or polymer) can be fed through the solid-
state additive
manufacturing system where frictional and adiabatic heating occurs at the
filler/substrate interface
due to the rotational motion of the filler and the downward force applied. The
frictional and
adiabatic heating that occurs at the interface results in a severe plastic
deformation at the interface
of the filler and substrate.
[0181] The filler materials can be in several forms, including but not
limited to any polymeric
form described herein, as well as: 1) metal or plastic powder or rod of a
single or composite
composition; 2) matrix metal and reinforcement powders which can be mixed and
used as feed
material; or 3) a solid rod of matrix which can be bored (e.g., to create a
tube or other hollow
cylinder type structure) and filled with reinforcement powder, or mixtures of
metal matric
composite and reinforcement material. In the latter, mixing of the matrix and
reinforcement can
occur further during the fabrication process. In embodiments, the filler
material can be a solid
metal rod. In one embodiment, the filler material is aluminum.
[0182] In embodiments, the filler material is joined with a substrate using
frictional heating
and compressive loading of the filler material against the substrate and
translation of the rotating
friction tool. The filler material can be a consumable material, meaning as
frictional heating and
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compressive loading are applied during the process, the filler material is
consumed from its
original form and is applied to the substrate. Such consumable materials can
be in any form
including powders, pellets, rods, and powdered-filled cylinders, to name a
few. More particularly,
as the applied load is increased, the filler material and substrate at the
tool-substrate interface
become malleable as a result of frictional and adiabatic heating and are
caused to bond together
under the compressive load.
[0183] The rotating tool can take a variety of forms. For example, the tool
can be configured
as described in any of U.S. Published Application Nos. 2008/0041921,
2010/0285207,
2012/0009339, and 2012/0279441, 2012/0279442, as well as International Patent
Application
Publication No. W02013/002869 and International Patent Application Publication
No.
W02019/089764, which published applications/publications are incorporated by
reference herein
in their entireties. Friction-based fabrication tooling for performing methods
of the invention are
preferably designed or configured to allow for a filler material to be fed
through or otherwise
disposed through an internal portion of a non-consumable member, which can be
referred to as a
throat, neck, center, interior, or through hole disposed through opposing ends
of the tool. This
region of the tool can be configured with a non-circular through-hole shape.
Various interior
geometries for the tooling are possible. With a non-circular geometry, the
filler material is
compelled or caused to rotate at the same angular velocity as the non-
consumable portion of the
tool due to normal forces being exerted by the tool at the surface of the tool
throat against the
feedstock. Such geometries can include a square through-hole and an elliptical
through-hole as
examples. In configurations where only tangential forces can be expected to be
exerted on the
surface of the filler material by the internal surface of the throat of the
tool, the feed stock will not
be caused to rotate at the same angular velocity as the tool. Such an
embodiment can include a
circular geometry for the cross-section of the tool in combination with
detached or loosely attached
feedstock, which would be expected to result in the filler material and tool
rotating at different
velocities. As used in this disclosure, the terms "additive friction-stir
tool", "friction-stir tool",
"non-consumable friction-stir tool", "rotating non-consumable friction-stir
tool" can be used
interchangeably.
[0184] In embodiments the throat of the tool can be shaped with a non-
circular cross-sectional
shape. Further desired are tooling wherein the throat of the tool is shaped to
exert normal forces
on a solid, powder, or powder-filled tube type filler material disposed
therein. Embodiments can
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also include features to ensure the frictional heating and compressive loading
are of a degree
sufficient to enable mixing of dispensed filler material with material of the
substrate at a filler-
substrate interface.
[0185] More specifically, the magnitude of force transferred from the
rotating tool to the filler
material is dependent on the coefficient of friction between the two. Thus, if
the coefficient of
friction is significantly low and the inertial force required to induce
rotation of the filler material
is significantly high, then the tool can rotate without inducing rotation (or
with inducing rotation
at a lower speed than the tool) in the cylindrical filler material. Under some
circumstances during
operation, differences in rotational velocity between the tool and the filler
within the tool can lead
to some filler material being deposited inside the tool, an accumulation of
which can be
problematic. Having the specific interior tool geometries can reduce this
issue, such as
appropriately sized square-square or elliptical-elliptical shaped filler-
dispenser geometries.
Another way of reducing the difference in rotational velocity between the tool
and the filler
material is to manufacture filler material rods to fit tightly within the
throat of the tool, or to
otherwise tightly pack the filler material into the throat of the tool.
[0186] Any shape of the cross section of the interior of the tool that is
capable of exerting
normal forces on a filler material within the tool can be used. The throat
surface geometry and the
filler material geometry can be configured to provide for engagement and
disengagement of the
tool and filler material, interlocking of the tool and feed material,
attachment of the tool and feed
material, whether temporary or permanent, or any configuration that allows for
the filler material
to dependently rotate with the tool.
[0187] The interior surface shape of the tool (the throat) and the
corresponding shape of the
filler material can be constructed in a manner suitable for a particular
application. Shapes of these
surfaces can include, but are by no means limited to, square, rectangular,
elliptical, oval, triangular,
or typically any non-circular polygon. Additional shapes can include more
distinctive shapes such
as a star, daisy, key and keyhole, diamond, to name a few. Indeed, the shape
of the outside surface
of the filler material need not be the same type of shape as the surface of
the throat of the tool. For
example, there can be advantages from having a filler material rod with a
square cross-section for
insertion into a tool throat having a rectangular cross-section, or vice-versa
where a filler material
rod having a rectangular cross-section could be placed within a tool throat
having a square cross-
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section in which the corners of the filler material rod could contact the
sides of the square throat
instead of sides contacting sides. Particular applications can call for more
or less forces to be
exerted on the filler material within the throat during operation of the tool.
With concentric shapes
and very close tolerance between the filler material and the tool certain
advantages can be realized.
Additionally, different shapes can be more suitable for different applications
or can be highly
desired due to their ease of manufacturing both the interior of the tool and
corresponding filler
material rods. One of ordinary skill in the art, with the benefit of this
disclosure, would know the
appropriate shapes to use for a particular application.
[0188] Additional embodiments of additive friction stir tools can include a
tool with a throat,
where the filler material and throat are operably configured to provide for
continuous feeding of
the filler material through the throat of the stirring tool. In embodiments,
the filler material is a
powder, the throat of the tool is a hollow cylinder, and an auger shaped
member disposed within
the throat of the tool is used to force powder material through the throat of
the tool onto the
substrate. The filler material can be delivered by pulling or pushing the
filler material through the
throat of the stirring tool.
[0189] Additional embodiments can comprise a tool or additive friction stir
tool comprising:
a non-consumable body formed from material capable of resisting deformation
when subject to
frictional heating and compressive loading; a throat with an internal shape
defining a passageway
lengthwise through the non-consumable body; an auger disposed within the tool
throat with means
for rotating the auger at a different velocity than the tool and for pushing
powdered filler material
through the tool throat; whereby the non-consumable body is operably
configured for imposing
frictional and adiabatic heating and compressive loading of the filler
material against a substrate
resulting in plasticizing of the filler material and substrate.
[0190] In embodiments, the tool and auger rotate relative to the substrate.
In further
embodiments, the tool and auger rotate relative to one another, i.e., there is
a difference in
rotational velocity between the auger and the tool body. There can be some
relative rotation
between the filler material and the substrate, tool, or auger. The filler
material and tool are not
attached to one another to allow for continuous or semi-continuous feeding or
deposition of the
filler material through the throat of the tool.
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[0191] For example, the filler material to be joined with the substrate can
be applied to the
substrate surface using a "push" method, where a rotating-plunging tool, e.g.,
auger, pushes the
filler material through the rotating tool, such as a spindle. Feed material
can be introduced to the
tool in various ways, including by providing an infinite amount of filler
material into the tool body
from a refillable container in operable communication with the tool.
[0192] In embodiments, the filler material is a powdered solid and is fed
through the tool body
using an auger shaped plunging tool (e.g., a threaded member). In such an
embodiment, the
plunging tool can be designed to move or "plunge" in a direction toward the
substrate. For
example, the threaded configuration of the auger itself is capable of
providing sufficient force on
the powdered feed material to direct the filler material toward the substrate
for deposition, without
needing vertical movement of the auger relative to the tool.
[0193] As the spindle and plunging tool rotate, compressive loading and
frictional heating of
the filler material can be performed by pressing the filler material into the
substrate surface with
the downward force (force toward substrate) and rotating speed of the additive
friction stir tool.
[0194] During the joining process, the spindle can rotate at a slightly
slower rate than the auger.
Alternatively, in embodiments, the spindle can also be caused to rotate faster
than the auger. What
is important in embodiments is that there is relative rotation between the
spindle and the auger
during application of the filler material. Due to the difference in rotational
velocities, the threaded
portion of the auger provides means for pushing the filler material through
the tool body to force
the material out of the tool toward the substrate. The threads impart a force
on the feedstock that
pushes the feed material toward the substrate much like a linear actuator or
pneumatic cylinder or
other mechanical force pushing on a surface of the feedstock. Even further, it
can be desired in
some applications to alter the rotational velocity of the tool body and/or
auger during deposition
of the filler material.
[0195] The deposition rate of the filler material on the substrate can be
adjusted by varying
parameters such as the difference in rotational velocity between the auger
screw and the spindle,
or by modifying the pitch of the threads on the auger. If desired, for
particular applications it can
be warranted to control filler material temperature inside or outside of the
tool body with for
example an external heat source. Such thermally induced softening of the
filler material can
increase the rate of application of the material.
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[0196] In the context of this specification, the terms "filler material,"
"consumable material,"
"consumable filler material", "feed material," "feedstock" and the like can be
used interchangeably
to refer to the material that is applied to the substrate from the additive
friction stir/solid-state
additive manufacturing tooling. In an embodiment, a powder filler material is
used in combination
with an auger disposed in the tool throat for applying a constant displacement
to the filler material
within the throat.
[0197] The filler material (for example, powder or solid feedstock) can be
fed through the
rotating spindle to exit the tool where frictional heating occurs at the
filler/substrate interface due
to the rotational motion of the filler and the downward force applied. The
frictional and adiabatic
heating that occurs at the interface acts to plastically deform the substrate
and filler material at the
interface resulting in a metallurgical bond or other bond between the
substrate and filler.
[0198] A mechanism can be used to feed powder into the spindle and force
the powder out of
the spindle while ensuring the filler is keyed into the spindle. This system
utilizes an auger screw
to force powder through the spindle at a defined rate, which is one means
capable of accomplishing
this purpose. Additional methods of feeding solid stock keyed into the
orientation of the spindle
and rotating at the exact rate of the spindle are conceivable. For example,
force can be applied to
the filler material using a metal rolling mill type mechanism which is
rotating with the spindle.
[0199] In such an embodiment, the spindle is spinning at a desired
rotational velocity and the
auger screw is driven at a different rotational speed in the same rotational
direction which acts to
force material out of the spindle. The angular rotational speed or velocity of
the friction stir tool is
identified as wl and the angular rotational velocity of the auger is
identified as w2. In the context
of this specification, the terms "rotational speed," "rotational velocity,"
"angular speed," and
"angular velocity" can be used interchangeably and refer to the angular
velocity of a component
of the tool during use. The auger screw can rotate at a slower speed than the
spindle, or the auger
screw can rotate faster than the spindle. What is important is that there is
relative rotation between
the spindle and auger to cause filler material to be forced through the throat
of the tool.
[0200] The pitch of the threaded auger screw and the volumetric pitch rate
of the screw will
affect the deposition rate under certain circumstances and can be modified to
accomplish particular
goals. It is within the skill of the art to modify the pitch of the threads on
the auger to obtain a
certain desired result. The terms "tool," "friction stir tool," "spindle,"
"tool body," and the like as
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used in this specification can be used to refer to the outer portion of the
tool body, which comprises
a passageway lengthwise through the tool for holding and dispensing feed
material through the
tool. This passageway, or throat, is generally the shape of a hollow cylinder.
The hollow cylinder
can be configured to have a wider opening at the top of the tool for
accommodating the auger and
powder material and a smaller opening at the base of the tool where the feed
material is dispensed
from the tool. Thus, the shape of the throat of the tool need not be
consistent throughout the length
of the tool throat and can be configured to converge from one lengthwise end
of the tool to the
other. The throat of the tool can comprise a first region which is the shape
of a hollow cylinder of
a first diameter. This region can transition into a second region which is the
shape of a hollow
cylinder of a second smaller diameter. The transition region can be a
converging hollow cylinder
or funnel shaped region to allow the first and second region to be connected
seamlessly.
[0201] Disposed within the tool body is an auger. In the context of this
specification, the terms
"auger," "screw," and "plunger" can be used to refer to a component of the
tool that is disposed
within the tool throat for pushing or pulling material through the throat. In
embodiments, the auger
can be considered a component of the friction stir tool body. The auger can
have the general shape
of a screw with threads or can be shaped in a spiral configuration similar to
a spring. When
disposed within the tool throat, there can be clearance between the auger and
the inside surface of
the tool throat to allow for the passage of feed material between the auger
and the throat. The inside
of the surface of the tool throat includes a sleeve and a bore. In other
embodiments, there is only
enough space to allow for rotation of the auger without interference from the
surface of the throat.
Preferably, the auger and tool body or spindle are not attached to one
another. Each is operably
connected with means for rotating and translating the components relative to a
substrate surface,
such that the auger and tool can rotate at different speeds but translate
relative to the substrate at
the same speed. The auger can be disposed within the tool throat in a manner
such that there is no
relative translational movement between the auger and tool body.
[0202] Powdered materials can be fed into the top of the spindle using a
fluidized powder
delivery system. Any type of powder delivery system can be used in connection
with the tools and
systems described herein. For example, a gravity-fed powder feeder system can
be used, such as a
hopper. One such feed system is the Palmer P-Series Volumetric Powder Feeder
from Palmer
Manufacturing of Springfield, Ohio, which is capable of delivering feed
material from 0.1-140 cu.
ft. per hour, and which comprises a flexible polyurethane hopper, stainless
steel massaging
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paddles, 304 stainless steel feed tube and auger, 90-volt DC gearhead drive
motor, flexible roller
chain drive system, sealed drive train and cabinet, and solid state control
and pushbutton controls.
The feed system preferably comprises a reservoir for holding powder filler
material, a mixer for
mixing powder(s) added to the reservoir, and a passageway for delivering feed
material from the
hopper to the throat of the tool body. As feed material is dispensed into and
from the tool, more
feed material is delivered into the tool from the hopper. In this manner, the
feed material is
continuously or semi-continuously delivered. The gravity-fed dispensing
systems allow for feed
material to automatically be dispensed from the hopper to the friction stir
tool during use as soon
as material within the tool is dispensed.
[0203] In embodiments, a mix of powder types can be added to the hopper
which is operably
connected with the stir tool. Alternatively, several different types of powder
can be added
individually to the hopper, then mixed within the hopper and dispensed as a
mixture to the friction
stir tool during use. For example, a metal powder and ceramic powder could be
fed into the spindle
at the same time, from the same or separate hoppers, and upon
consolidation/deposition the filler
would be a metal matrix composite (MMC). As used herein, the term "metal
matrix composite"
means a material having a continuous metallic phase having another
discontinuous phase dispersed
therein. The metal matrix can comprise a pure metal, metal alloy or
intermetallic. The
discontinuous phase can comprise a ceramic such as a carbide, boride, nitride
and/or oxide. Some
examples of discontinuous ceramic phases include SiC, TiB2 and A1203. The
discontinuous phase
can also comprise an intermetallic such as various types of aluminides and the
like. Titanium
aluminides such as TiAl and nickel aluminides such as Ni3A1 can be provided as
the discontinuous
phase. The metal matrix can typically comprise Al, Cu, Ni, Mg, Ti, Fe and the
like. Similarly, a
metal powder and plastic powder, or ceramic powder and plastic powder, can be
fed
simultaneously, at different times, from the same hopper, or from separate
hoppers.
[0204] The present invention has been described with reference to
particular embodiments
having various features. In light of the disclosure provided above, it will be
apparent to those
skilled in the art that various modifications and variations can be made in
the practice of the present
invention without departing from the scope or spirit of the invention. One
skilled in the art will
recognize that the disclosed features may be used singularly, in any
combination, or omitted based
on the requirements and specifications of a given application or design. When
an embodiment
refers to "comprising" certain features, it is to be understood that the
embodiments can
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alternatively "consist of' or "consist essentially of' any one or more of the
features. Other
embodiments of the invention will be apparent to those skilled in the art from
consideration of the
specification and practice of the invention.
[0205] It is noted in particular that where a range of values is provided
in this specification,
each value between the upper and lower limits of that range is also
specifically disclosed. The
upper and lower limits of these smaller ranges may independently be included
or excluded in the
range as well. The singular forms "a," "an," and "the" include plural
referents unless the context
clearly dictates otherwise. It is intended that the specification and examples
be considered as
exemplary in nature and that variations that do not depart from the essence of
the invention fall
within the scope of the invention. Further, all of the references cited in
this disclosure are each
individually incorporated by reference herein in their entireties and as such
are intended to provide
an efficient way of supplementing the enabling disclosure of this invention as
well as provide
background detailing the level of ordinary skill in the art.
